Process of producing color on textile materials



- tented Sept. 17, 1940 v PBOCESS'OF PRODUCING COLOR" 0N 1 a TEXTILE'MATERIALS s Paul Schlaclr, Berlin-flreptow, Germany,

to'General Aniline &

poration of Delaware Film Corporation, a coi'-,

No Drawing. 1 Application September 14, 1937, Se

rial No. 163,742. In

1936 14 Claims.

It is an object of this invention to'provide a process by which artificial filaments or foils which have little or no swelling capacity in water and which are generally soluble in organic solvents may be dyed in fast tints and with surprising brilliancy of color.

A further object is to produce delustering of fibers of the kind referred to above by precipitatlng therein white metallic precipitates.

These and further objects will be apparent from the following specification.

Attempts have frequently been made to color fibrous materials, foils etc. produced from highly polymeric bodies which have little swelling capacity in water by producing upon them white or colored precipitates of inorganic materials or by causing inorganic metal compounds to react with organic substances which, without themselves having the character of dyestuif, yield with the metallic compound an opaque or colored precipitate, particularly one having the characteristic of a complex salt.

However, these. attempts, at least in so far as they have dealt with individual colors, have not achieved results of any value since the precipitates, for example those produced by bichromate, lead sulfide or iron compounds of the nitrosonaphthols have proved insuificiently fast. Moreover, such colorings lack brilliance.

The present invention produces colorings which are in part thoroughly fast. and in part of surprising brilliance by producing on or in threads, films, or the like, made from hydrophobic organophilic highly polymeric products which contain polar salt-forming relatively hydrophilic but also highly molecular polymeric components, white or colored precipitates of metals or metal compounds of a pure inorganic nature or precipitates of metal compounds and organic substances without particular dyestufi' characteristics. Suitable organophilic filmor fiber-forming polymeric products are for instance cellulose esters, cellulose ethers, cellulose ether esters, polymeric vinyl esters, especially the ones made soluble in acetone by after-chlorination (see U. S.

Patent No. 1,982,765 to Schdnburg), polymeric vinyl-ketOnes and other polymerizates and mixtures thereof with cellulose derivatives.

Additions to the main substance of these sub- Germany September 23,

strata which are suitable for the process of this invention are, for example, resins of high molecular weight with a number of carboxyl groups, particularly polymerizates from unsaturated carboxylic acids or poly-carboxylic' acids or mixed poly-' merizates of such carboxylic acids and compounds having active double linking, for instance the mixed polymerizates from organic or inorganic esters of vinyl alcohol, like vinyl chloride, vinyl formate, vinyl acetate, vinyl chloracetate or from vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether, from acrylic acid or methyl acrylic acid esters, nitriles or amides, styrene and acrylic acid, maleic acid, maleic ester acid, maleic anhydride, itaconic anhydride. Furthermore there belong here the mono-esters, soluble in organic solvents, of polyhydroxyl compounds with dior poly-carboxylic acids, for example the esters are obtainable by the action of succinic [acid anhydride, nonylene succinic acid anhydride, maleic anhydride 'or phthalic anhydride on organic cellulose derivatives still containing hydroxyl, for instance methyl cellulose, ethyl cellulose or acetyl cellulose or on synthetic polyhydroxyl compounds, for instance partially acetylated vinyl alcohol.

Compounds of this kind have already been described in U. S. patent application Ser. No. 57,524 filed January 4, 1936.

There also come into question for the process resins or derivatives of natural highly polymeric bodies with a number of basic groups in the 'molecule, forinstance basic artificial resins ofthe polyvinyl series, like polyacrylic acid-omega diethylaminoethylamide, basic derivatives of p'olyglycide, basic cellulose derivatives, for instance diethylaminoethyl cellulose or an ester or ether thereof, provided such resin or other compound is soluble in the solution or a constituent of the solution used for forming the shaped structure or is at least capable of sufficiently homogenous dispersion therein. Products of this kind are described in U. S. patent application Ser. No. 47,638 filed October 31, 1935 and U. S. patent application Ser. No. 64,776 filed February 19,1936.

It is not necessary that the basic or acid residues'should be obtained from the first in a free form in the structure. Alternatively, they may be, and indeed in many cases with particular advantage, formed or liberated only'subsequently, for example by an after-treatment With'a hydrolizing, alkylating or-aminating agent in the case of basic groups and by treatment'with hydrolizing or oxidizing agents in the case of acid groups. In this connection reference is also made to the above named applications. However, the present process is not limited to the fibers and foils with additional components named as examples therein. a

The substrata suitable for the present invention also contain both acid and basic salta-forming groups. Thecombination of a'cid and basic groups in the structure increases considerably the reactivity and leads to particularly intense and 1 manifold effects, since the primary component may be made to combine with acid orbasic groups at choice. If desired both functions can be uti- .1 lized simultaneously, whereupon the reaction may be produced within the structure :by varying the pI-I-value by heating, by steaming or by the action of an oxidizlng agent. In practice very varied color effects are obtainable, for'example inyarn invention are, for example, as follows: 7

1. The reaction of a heavy metal combined with an acid group in the structure, for instance mercury, silver, lead, copper, cadmium, iron, cobalt, nickel or uranium with dissolved or gaseous sulfuretted hydrogen, a soluble sulfide, for instance ammomumsulfide, sodium hydrosulfide, magnesium hydrosulfide or with a material which easily yields sulfur, for instance thioureaor hypo- 2. The reaction of a heavy metal combined in the fiber with a ferrocyanide or a ferricyanide, for instance the reaction of zinc or copper or trivalent iron with potassium ferrocyanide or the reactiion of divalent iron with potassium fen-icyan de.

3. The reaction of chromic acid united with a basic group with a lead salt or a barium salt and vice versa the reaction of lead or barium wi chromic acid.

4. The reaction of a heavy metal united by an acid group to the fiber with an organic substance, capable of forming a color complex, which is not itself a dyestufi, for example a p-dicarbonyl compound, a hydroximino-ketone, an a-dioxime, an amido-oxime, a hydroxyamido-oxime, a polyhydric phenol, a hydroxy-quinoline, a nitrosoarylhydroxylamine, a thioglycolic acid arylide. As individuals there may be named anisoylbenzoylmethane, hydroxymethylene camphor, the diimine from ethylene-diamine and 2 mol acetylacetone, isonitrosoacetoacetic acid anisidide, the

, isonitroso-compound of acetone-oxalic acid ester a particularlydecply seated effect is desired, be

assisted by a swelling agent, such as acetone, al-- oohol, acetic acid, phenol, a sulfocyanide, thiourea or pyridine; also weakly basic substances, which otherwise have no particular swelling properties,.like urea, have ag od, efl'ect, especially in .thecase of structures having carboxyl groups.

The swelling agent must be selected so that no insoluble precipitate may be formed with the components that are to react and that further the materials added in the structures are not dissolved and washed ofl. In some cases dissolution may beprevented by the addition of a substance [which prevents' or diminishes solubility. Such substances are, in the case of acid groups, for instance calcium salts or zinc salts, also amines or ammonium salts 'of high molecular weight. In the case of basic components, such as alkylnaphchloracetic acid and their salts come into consideration, These substances,=however, must not be present in toohigh'a proportion in sofargas they are not veryeasilyexchangeable for thereacting components.

-Finally, the absorptivencapacityof the ture, so ,far as-it contains groups capable of elimination by hydrolysis, 1 may be enhanced by a saponifying agent, for; example an alkali, asalt of alkaline reaction, ammonia or anamine'. Preferably saponification should not-proceed to the .7

material of the substratum, but should substantially be limited to the salt -forming component.

The order in which the double decompositions of the, components are to be brought about is fundamentally indiiferent. It is necessary in each A case to ascertain by suitable experiment what is the best procedure. And so also the iworkingconditions, such as the pH-value of the liquor," the temperature, the kind and proportion of the added substances, for example, the addition'of salt-must be adapted for each reaction. Further it is necessary that in reactions which producethe conversion of a' dissolved substance to an insoluble coloring or matting precipitate, to'add a dispersing agent, such as oleylpolyglycol, quaternarycapillary active ammonium compounds and if desired also a protective colloid whereby an improvement of the fastness to rubbing is obtained and the dirtying of .uncolored components in mixed fabrics may be avoided as far as possible.

The operation of introducing a component by a dyeing operation or otherwise may with advantage follow directly on the production of the shaped structure. For example, acetate silk which contains the aforesaid maleic anhydride mixed polymerizate in a proportion of 5 to 15 per cent may be treated in the spinning machine or in the precipitating bath with a metal salt such as copper acetate, cobalt acetate, nickel acetate or iron nitrate. It is also practicable to treat in a later operation, for example in spinning the material in the form of a wound bobbin, cross-spinning or the like, with a solution of the salt in question, it being advantageous to add also urea or another agent that activates the carboxyl group. In making staple fiber the mordant may be applied during the spinning or immediately afterwards or in combination'with a wet aftertreatment, for instance for the'purpose of crimping. The process has the advantage over dyeing.

during spinning that a whole number of fast tints inany depth may beiobtainedwith one and the same spinning solution in a simplemanner;

There exists also the possibility of adding one or another component to a preparatory solution,

in which case difl'erent developments give rise to numerous possibilites of variation. Finally the structure may contain from the spinning onwards white or colored pigments, for example, 1 per cent of titanium dioxide or 0.2-1 per cent of carbon black. A comparatively small additionof black is advantageous, particularly in cotton material which is intended for admixture with wool for the cloth industry, in which casefull color tints are deemed desirable, this being attainable by the after-treatment according to the invention of the fiber which has been colored black during the spinning.

Very deep tints are obtained in many cases by a single treatment. Where this is not the'case, the treatment may be repeate d once or several times until the absorptive capacity of the fiber is exhausted. Mixed tints are obtained by simultaneous use of several grounding or development processes or by successive independent coloring operations. Finally any combination with other known dyeing or coloring methods comes within the limits of the invention.

The process is not only applicable to dyeing, but also with advantage to printing. Thus a fabric of acetate silk to which has been added a maleic anhydride mixed polymerizate may be impregnated with a metal salt, for instance a copper or a nickel salt and after rinsing and drying may be printed with different complexforming substances, for instance 1-nitroso-2- naphthol, dimethyl-glyoxime, hydroxymethylene camphor or 4-nitrobenzhydroxamic acid. On the other hand, bottom dyeings may be produced on the goods and these over-printed withany organic dyestuil' suitable for the material, accompanied in suitable cases with .white discharge or color discharge effect.

with copper acetate and then dyed green with dimethylglyoxime and then discharged by means of a paste containing a strong acid such as oxcombines in a complex manner the cation liberated by the discharge and thus to prevent its being again taken up by the fiber during rinsing. The paste may also contain a compound which destroys by oxidation or by reduction or makes ineffective by condensation the organic liberated complex former. This may be achieved by means of potassium chlorate or aluminium chlorate or hydrosulilte or a carbonyl reagent, such as benzhydrazide, semi-carbazide or hydrazine sulfonic acid. As an oxidizing agent an alkyl halide derivative or sulfonamide may be used. For example, a fabric of acetate silk having an acid component which, after a grounding with a copper salt was developed with potassium ferrocyanide to a red-brown tint, is discharged by means of a paste which contains ethanolamine or the like. To this paste may also be added a dispersion dyestufl or acetate silk so that a color discharge is possible. The same effect is obtainable by printing a compound which reacts of the invention are thoroughly fast to washing;

in many cases, however, an improvement follows Thus "a cellulose acetate fabric having acid groups may be pretreated if the dyed filaments are after-treated with a water-repelling agent that diminishes the swelling.

In the case of structures having acid groups such an after-treatment may consist in saturating the still free carboxyl groups as far as is possible with cations, preferably colorless, which have a tendency to form sparingly soluble compounds, for example magnesium, calcium, barinents having different lengths of chain, since in 20 this manner an especially good depth of action and at the same time a very favorable effect on the feel of the material, owing to the accumulation of the constituents of highest molecular weight on the surface. The after-treatment with amines or their salts is particularly useful when the deposited metal compound, for instance of colored metal sulfide, has a certain tendency for autoxidation, especially in presence of moisture. The protective effect of the amines extends both to the diminution of the hygroscopic tendency and the anti-oxidizing eflect. In many cases it has been found advantageous to provide a treatment in which instead of the simple amine or in addition to the amine there is used a particularly strongly acting anti-oxidizing agent, especially one which has a tendency to combine with traces of liberated metal ions, for example an arylmercaptan, a mercaptoalkylamine, mercaptobenzothiazole, an alkylor aryl thio-semi-carbazide, thiourea, a polyhydric phenol or an oxime.

In the case of structures having a basic character an anionic agent is suitable for diminishing the capacity for swelling, for instance aperchlorate, a trichloracetate, a fatty alcohol sulfonate, a sulfonic acid. of high molecular weight of the aliphatic or aromatic series.

The invention is not limited to structures consisting of one or. more components, although in general the best results are obtained with such materials. The reactive salt-forming groups may also be produced by an after-treatment with an oxidizing-agentf r a basic aminatingagent in an individual material during or after the shaping operation. Reactions of this kind, for example, the reaction of ethylene imine vapor on acetate silk or the reaction of acetyl cellulose in dioxane solutionwith diethylamine epihydrin directly before the spinning, also the oxidation of threads from hydroxyethylated acetate silk by means of strong oxidizing agents, such as potassium permanganate.

- The following examples illustrate the invention: v a

1. An acetate silk satin fabric, the warp of which consists of stripes of ordinary acetate silk alternating with stripes of acetate silk having 10 per cent of a mixed polymerizate from 1 mol vinylmethyl ether and 1 mol maleic anhydride is treated after having been desized with soap solution and without'an intermediate acid treatment in'a liquor ratio of 1:40 with an aqueous solution of'10 per cent strength of copper acetate for A hour at 60 C. The strips of the silk which contain resin now have a relatively powerful blue-grey color. After a short rinsing the fabric is immersed in a solution of ammonium sulfide of 1 per cent strength at room temperature, whereby the color is gradually developed through brown to greenish black. The portions consisting of ordinary acetate silk are reserved white. The black effect obtained is fast to rubbing and washing.

The development may be interrupted if desired when the brown tint has been produced. However, it is then necessary to remove completely any unattacked copper or to convert the latter into a non-dissociated compound so that autoxidation may be avoided. It is therefore in this case more advantageous to use in the pre-treatment a weaker solution of copper salt or in working with a standing bath of correspondingly higher concentration to shorten the duration of the treatment.

When particularly strong coloring is desired the treatment may be repeated.

2. The goods grounded with copper acetate in the manner described in Example 1-are developed at 50 C. with 2 per cent of dimethylglyoxime. There is obtained an apple green color.

' 3. The goods are grounded as described in Example 1 with a solution of potassium forrocyanide. There is obtained a brown-red color.

4. The goods grounded as described in Example 1 are developed with anthranilic acid. There is obtained a green pastel tone.

5. The goods grounded as described in Example 1 are developed with salicylic acid. There is produced a clear blue green.

6. The goods grounded as described in Example.

1 are developed with cupferron (nitrosophenylhydroxylamine). There is obtained a stone in green pastel tone.

7. The goods grounded as described in Example 1 are developed with 4-nitrobenzhydroxamic acid. A grass-green color is produced.

8. The fabric used in Example 1 is treated for 1% hours at 75 C. with 20 per cent of ferrous ammonium sulfate in presence of 0.5 gram of oleyl-polyglycol and then developed at 60 C. with 2 per cent of nitrosonaphthol. There is produced a fast olive green color (pigment green).

9. The goods grounded as described in the preceding example are developed in a solution of potassium ferricyanide whereby a very pure brilliant greenish blue is produced (Turnbulls blue). The white is only very little tinted. If the process is reversed by first mordanting with ferric nitrate and developing with potassium ferrocyanide there is obtained a dull blue-green.

10. Acetate silk containing 12.5 per cent of the mixed polymerizate from vinylethyl ether and there is obtained a field grey tint.

12. A- fabric of acetate silk, the warp of which consists of alternating strips of acetate silk containing 10 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride, ordinary acetate silk and acetate silk having 10 per cent of-polyvinylchloracetate is desized and pretreated as described in Example 1 with 20 per cent of cadmium acetate. By immersing the fabric in dilute ammonium sulfide solution there is obtained an intense rather brilliant yellow, fast to light rubbing and Washing .on those strips which contain a maleic anhydride polymerizate. The two other components remain uncolored. If

'now the fabric is treated by the process of U. S.

patent application Ser. No. 41,500 filed September dine vapor, calculated as equivalent to the halogen present, and then dyed with 2 per cent of Indigosol Green IB (Schultz Farbstofitabellen, 7th Ed., vol. 2, page 133) by the nitrite process there is obtained a yellow-white-green stripe effect which is fully stable to light. Cadmium yellow, as is shown by a cross-section of the filaments, is thoroughly distributed in the latter.

13. An acetate silk having 7.5 percent of polyvinylchloracetate and 7.5 per cent of the mixed polymerizate from 1 mol of maleic anhydride and 1 mol of vinylformate is soaped at 80 C. and aminated in toluene with three times the quantity of pyridine, calculated as equivalent to the halogen. The fabric is then mordantedwith 20 per cent of ferrous ammonium sulfate at 40-'75 C. and finally dyed simultaneously with 2. per cent of Sirius Light Yellow (Schultz Farbstoif tabellen, 7th ed., suppl. vol., page 131) and 3 per cent of isonitroso-fi-naphthol at a temperature between 40 and 80 C. There is obtained a yellow-green dyeing of good properties of fastness.

14. A mixed fabric containing in addition to ordinary acetate silk an acetate silk having 12.5 per cent of the mixed polymerizate from vinyl formate and maleic anhydride is primarily dyed with 3 per cent of Celliton Fast Yellow (Schultz Farbstofftabellen, 7th ed., vol.- 2, page in the usual manner; it is then mordanted with copper acetate and developed with ammonium sulflide. There is produced a very good two-color efiect in yellow and black.

15. An acetate silk mixed fabric similar to that used in Example 1 is dyed in the usual manner.-

After a further treat-:-

' 20, 1935 with three times the quantity of pyristripes on a reddish-yellow ground. The dyeing is very fast to washing.

16. Acetate cellulose which contains 12.5 per cent of the mixed polymerizate from maleic anhydride and vinyl formate is pro-treated in the course of hour with 10 per cent of cobalt acetate. The color is developed with ammonium sulfide. The deep black material is now finished with 2 per cent of a mixture of dodecylamine acetate and 1 per cent of octadecyltrimethylammonium chloride and can be used in admixture with white wool. t 1

17. Acetate silk which contains 10 percent of the mixed polymerizate of vinylmethyl ether and maleic anhydride is treated with 5 percent of 'tetra-'y-chloro-p-hydroxypropyl ammonium acepears. By after-treatment with copper ace ate 75 solution the previously wetted silk takes up copper freely. The goods developed with ammonium sulfide may then be printed-with dyestuffs con- 10 per cent of the mixed polymerizate from vinylmethyl ether and. maleic anhydride is mordanted with 10 per cent of cobalt acetate at 60 C. The metal is freely taken up.. By developing with diphenylthiocarbazone there is obtained an intensely brownish-violet tint.

19. A satin fabric, the warp of which consists of alternating stripes of an acetate silk mordanted witli'cobalt acetate and containing 10. per

cent of the mixed polymerizate from 1 mol vinylmethyl ether and 1 mol maleic anhydride, of ordinary acetate silk and of acetate silk containing 12.5 per cent of the aforesaid polymerizate but without having been mordanted with a metal salt, is first desized in a soap bath' and then immersed in ammonium sulfide solution of 1 per cent strength, whereby the first named stripes are colored deep black with cobalt sulfide. The goods are now mordanted with nickel acetate and finally developed with 2 per cent of dimethylglyoxime in presence of sodium acetate, whereby the third named stripes are dyed scarlet red. The goods are finally brightened with a mixture of quarternary ammonium compounds on the alkylbromide mixture from palm nut fatty alcohol and trimethylamine.

20. An acetate silk containing 10 per cent of the mixed polymerizate from acrylic acid and vinyl acetate is treated with chromium acetate solution at 40 'to 60 0., there being preferably added ammonium sulfocyanide. The pre-mordanted fiber is dyed deep brown with 4 per cent of dlnitroresorcinol.

' 21. Asatin fabric of acetate silk containing 10per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride (1:1) is grounded with l per cent of silver acetate, preferably in presence of a desensitizer, at 60 C. By treatment with sodiumphosphate the mordanted fabric becomes first yellowish in the cold, on warming the color turn towards a violetish brown. With hydrogen sulfide there is obtained a brown tone. By exposure to light alone there is produced a brownish silver tone which. by treatment with sodium selenosulfate becomes reddish. By exposing through a negative half-tone images are obtained. In this case the sensitiveness is advantageously enhanced by addition of a sensitizer.

22. A patterned mixed fabric which consists in part of ordinary acetate silk and inpart of acetate silk having an addition of 10 per cent of the mixed polymerizate from vinylformate and maleic anhydride (1:1) is pre-mordanted with 10 per cent of zinc acetate for 1 hour at 60 C. By developing with potassium. ferrocyanide there is obtained a beautiful matt eifect which may be top-dyed with basic dyestuffs in the cold without loss of luster. l

23. The same acetate silk as is used in the preceding example is grounded with 10 per cent of barium acetate.

strong matt effect. The barium sulfite thus formed is oxidized by the air to barium sulfate.

By immersing the silk in dilute sodium bisulfite solution there is obtained a very 26. The fabric grounded. as described in the preceding example with lead-acetate is developed with potassium iodide solution. There is produced a reddish gold-yellow.

27. An acetate silk containing 6 per cent of polyvinylchloracetate and 6 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride (1:1) is treated in a liquor ratio of 1:40 in an aqueous solution of 20 per cent of barium sulfocyanide and 8 per cent of N-cyclohexyl- N'-dimethylthiourea dispersed with oleyl polyglycol, the treatment being for 2 hours at 70 to C. In this manner the fiber is aminated with formation of an isothiourea ether group. Simultaneously the barium and sulfocyanogen ions are bound. By after-treatment with weak acidified sodium hydrochloride solution barium sulfate'is formed in the fiber. If, simultaneously, the fabric is dyed with a basic dyestufi stable to oxidation there is obtained a matt dyeing.

28. The same fabric as is used in the preceding example is aminated with pyridine and treated with barium methylsulfate. By raising the temperature to 85 to C. barium sulfate is formed by hydrolysis within the fiber.

29. The same acetate silk as is used inthe preceding example is aminatedwith pyridine and then dyed with 2 per cent of Indigosol Green 128 (Schultz Farbstofftabellen, 7th -Ed., vol. .2, page.

133) and the dyeing is developed in the usual manner by means of chromic acid. By aftertreatment of the dyed silk with lead acetate chrome yellow is produced on the fiber. The tint is yellow-green. The chromate may be dyed on the fiber'under neutral conditions simultaneously with the Indigosol and the dyeing developed by a treatment with acid.

30. The warp of an acetate silk fabric which contains 12.5 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride.

polyvinlychloracetate and 5 per cent of the mixed polymerizate from maleic anhydride and vinylform'ate (1 :1) is first treated with pyridine at 40 to 50 C. and then with a barium sulfocyanide solution of 2.5 per cent strength, containing 5 per cent of urea. The goods are finally oxidized with hydrogen peroxide solution, whereby barium sulfate is produced within the fiber.

32. Acetate silk which contains 12.5 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride (1:1) is first thoroughly soaped and then treated with 20 per cent 75 of zinc acetate for ihour at 60 C. for the purpose of activating the carboxyl groups. After treatment with sodium hyposulfite zinc sulfide is formed in the fiber. The material obtains a matt appearance. If a mixture of zinc acetate and cadmium acetate is used there is obtained by treatment with hyposulfite a yellow pastel tone. l

33. A satin fabric in which the warp consists of alternating stripes of ordinary acetate silk and acetate silk with an addition of 10 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride (1:1) is treated-with 10 per cent ofmanganese acetate for 1. hour at 65 to 70 C. After rinsing the color is developed by means of potassium permanganate. Thereis obtained a lustrous deep brown effect on a slightly dyed ground.

34. An acetate silk containing polyvinylchloracetate, aminated with 10 per cent ofpyridine on the fiber is thoroughly rinsed and then treated with sodium sulfate and 3 per cent of potassium permanganate at room temperature. The fabric is uniformly colored brown. After soaping the color is brilliant and fast to rubbing. It can be discharged white by means of oxalic acid.

35. An acetate silk which has been treated for 8 hours at 70 C. and 92 per cent of relative atmospheric moisture with 15 per cent of ethylene imine vapor is grounded with 2 per cent of potassium bichromate for 1 hour at40 to 50 C. whereupon the dyeing is developed with 10 per cent of lead acetate.

36. An acetate silk containing 7.5 per cent of polyvin'ylchloracetate and 5 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride is caused to react with an excess of pyridine in the gaseous phase and pre-mordanted with 3 per cent of potassium bichromate at 40 to 60 C. The silk is again rinsed and then immersed in a liquorcontaining 10 per cent of lead acetate, calculated on the weight of the goods, and 200 grams of acetone per liter. The original lustrous silk is in this manner colored an intense matt yellow by formation of chrome yellow in the fiber. After thorough soaping the goods are finally finished with octadecyltrimethylanmioniumacetate. Instead of acetone alcohol or dioxane may be added to the lead acetate solution. The coloring is completely fast to washing and of good fastness to rubbing. In spite of the content of pigment the silk is soft to feel and remains smooth.

3'7. The same silk as is used in the preceding example is first soaped in the form of compact bobbins ina dyeing apparatus for 2 hours at 65 C. with 5 grams of soap per liter and then, after rinsing, treated in the same apparatus with a 10 per cent solution of lead acetate at 60 C. The fiber takes up much 1ead, as can be followed by observing the blackening produced by ammonium sulfide solution. The fiber thus mordanted with lead is now suspended over pyridine and aftertreated with ammonium bichromate at 30 to 60 C, The very uniform coloring is this time lustrous owing to the soaping. The treatment with pyridine may also precede the treatment with lead acetate. In this case there is no soaping, but there should be added to the lead acetate solution 10 per cent of urea, calculated on the weight of the silk.

38. An acetate silk, which in addition to parts of acetone soluble acetyl cellulose having 52 per cent of combined acetic acid contains 20 parts of acetone soluble acetyl cellulose monophthalic acid, obtained by reaction of an acetyl cellulose having 50.8 per cent of combined acetic acid and phthalic anhydride, is mordanted for 1' hour at 75 C. with 20 per cent of copper acetate in presence of 1 gram of sodium 'oleylmethyltaurine. By after-treatment with 3 per cent of salicyl aldehyde oxime there is obtained a green I dyeing.

39. A film of cellulose ethyl ether having 41 per cent of ethoxyl and containig 8 per centof polyacryllc acid-omega-diethylaminoethylamide is treated with 3 per cent of potassium bichromate for 1 hour at 30to 50 C. The dyeing is developed with an aqueous solution containing:

per liter 200 grams of alcohol and 25 grams of lead acetate. The color isdeveloped-at 30 to 40 C. When the color no longer increases the goods are washed and soaped.

40. A solution consisting of 20 parts of acetyl cellulose having 54 per cent of combined acetic acid, 2 parts of the mixed polymerizate from vinylformate and maleic anhydride (1:1), 0.05 part of a-nitroso-fl-naphthole and 75.5 parts of acetone is spun to acetate cellulose threads. After cutting to staple length the material is treatedv ing 12 per cent of the mixed polymerizate from.

vinyl chloride and maleic anhydride (1 :1), is first immersed for 2 hours in a 0.5 per cent aqueous solution of triethanolamine at 30 C. and is then treated with copper acetate solution of 5 per cent strength for 2 hours at 40 to 50 C. By aftertreatment with an alkaline solution of acetone oxalic ester imine there is obtained a beautiful green color.

I 42. Acetate silk containing 10 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride is printed at intervals on the running thread with a paste thickened with tragacanth and containing tetrammine cadmium hydroxide and tetrammine cupric hydroxide and urea. By after-treating the fabric made from this yarnwith ammonium sulfide-solution-there is obtained a black-white-yellow ombr effect.

A similar process can also be applied in printing yarn or warp, for which the process of the invention is essentially better suited owing to the free penetration of the agents than the dyeing method with dispersion dyestuffs insoluble in water which, as a rule, require prolonged steaming. Since in the developing of the dyeings in the present process comparatively low temperatures are sufiicient, pure effects of this kind are easily obtained, also with the wax reserve method.

43. To a solution of dimethyl cellulose in a mixture of methylene chloride and methanol (85:15) there is added 8 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride (1:1), calculated on the quantity of the cellulose ether. The film obtained from this solution after pre-treatment with 0.5 per cent of trlethanolamine solution at 30 C. is mixed in a per cent nickel acetate solution for 2 hours at 80-65? C. By after-treatment with dimethylglyoxime in ,the presence of sodium acetate there is obtained a red dyeing.

44'. A fabric of acetate silk containing 10 per cent 01 the mixed polymerizate from vinylmethyl ether and maleic anhydride (1:1) is printed with a paste consisting essentially of an acid tartaric acid solution of polyethylene mine or an oxyethyl derivative thereof. The copper is bound in complex union on the parts printed with the discharge paste, so that ,the printed parts re- .main practically uncolored on development with ammonium sulfide. For the binding or copper in complex union there are specially'suitable amineswhich are substituted by several omega-carboxymethyl-radicals, such as for instance tris- [omega-carboxy-methyl-J amine.

45. An acetate silk containing originally 7.5 per cent of polyvinylchloracetate and 7.5 per cent of the mixed polymerizate from vinylmethyl ether and maleic anhydride (1:1 aminated with pyridine is first pretreated in presence of urea with 5 per cent of titanium potassium oxalate and then after-treated with a 5 per cent solution of basic ferrous acetate. There is obtained simultaneously a pigmentation with titanic acid and a color which may be well washed, by the adsorption of iron. The goods are finished with 2 per cent of dodecylguanidine.

The process may, asstated elsewhere herein, and as indicated in the examples, be combined with many known methods of dyeing. In the case of already dyed material there is the advantage that the top-dyeing with the agents of this invention is possible in most cases without prejudice to the first dyeing. This condition is particularly important in the case of acetate silk, since the typical acetate silk dyestufis are, as a rule, only moderately top-dyed. Finally, it may be remarked that already existing dyeings may be improved in their properties of fastness by a topdyeing by the process of the invention which, doubtless, is to be attributed to the fact that insoluble substances introduced hinder diffusion on' ing group, which process comprises forming a precipitate of .an' insoluble metal compound on said textile materials and foils.

2. A process of producing colorings on the untreated artificial textile materials and foils of claim 1, which process comprises forming an in-' which process comprises forming a precipitate or an insoluble metal compound on said textile materials and foils.

4. A process of producing colorings on artificial textile materials and foils, said textile materials and tolls comprising one of the group of organophilic colloids consisting of-cellulose ethers,

' cellulose esters, cellulose ether esters, polymeric said textile materials and foils in the presence of 1 a swelling agent.

5. A process of producing colorings on artificial textile materials and foils, said textile materials and foils comprising one of the group of organo- 0 philic colloids, consisting of-cellulose esters, cellulose ethers, cellulose ether esters, polymeric vinyl esters, after-chlorinated polymeric vinyl esters, polymeric vinyl ketones and mixtures of these substances-and having incorporated and fixed therein an artificial resin with a salt-forming group, which process comprises forming a precipitate of an insoluble metal compound on said textile materials and foils in the presence of a dispersing agent.

6. A"process of producing colorings on the untreated artificial textile materials and foils of claim 1, forming aninsoluble precipitate of a meta1 compound and after-treating said materials with a compound capable of forming an insoluble hydrophobe salt with said salt-forming group.

7. A process of producing colorings on artificial textile materials and foils, said textile materials and foils comprising one of the group of organophilic colloids consisting of-cellulose esters, cellulose ethers, cellulose ether esters, polymeric vinyl esters, after-chlorinated polymeric vinyl esters, polymeric vinyl ketones and mixtures of these substances-and having incorporated and fixed therein an artificial resin having in its molecule acid groups, which process comprises treating said textile materials and foils with a carbamide and forming thereon an insoluble precipitate of a colored metal compound of an organic substance which has not per se the charactor of a dye.

- 8. A process of producing colorings on artificial textile materials and foils comprising one of the group of organophilic colloids consisting of cellulose esters, cellulose ethers, cellulose'ether esters, polymeric vinyl esters, after-chlorinated polymeric vinyl esters, polymeric vinyl ketones and mixtures of these substancesarid having incorporated and fixed thereon an artificial resin having in its molecule acid groups, which process comprises forming a precipitate of an insoluble metalcompound on said textile materials and foils and aftep-treating said textile materials and foils with a salt of a metal of the group consisting of magnesium, calcium, barium, aluminium, zinc, cadmium, lead, copper, nickel, cobalt, manganese and silver.

9. A process of producing colorings on the untreated artificial textile materials and foils of claim 8, which process comprises treating said textile materials and foils with an alkaline agent and forming thereon a precipitate of an insoluble metal compound on said textile materials and toils.

10. A process of producing colorings on artificial textile materials and foils comprising one of the group of organophilic colloids consisting of cellulose esters, cellulose ethers, cellulose ether esters, polymeric vinyl esters, after-chlorinated polymeric vinyl esters, polymeric vinyl ketones and mixtures of thesesubstances-and having incorporated and fixed therein an artificial resin having in its molecule acid groups, which process comprises forming a precipitate of an insoluble metal compound on said textile materials and foils and after-treating said textile materials and foils with an organic base of the group consisting of ammonium-, phosphonium-, sulfonium-bases, guanides and biguanides, said organic base having in its molecule a carbon chain of from 8 to 14 carbon atoms.

11. A process of producing colorings on artificial textile materials and foils, said textile materials and foils comprising one of the group of organophilic esters, cellulose ethers, cellulose ether esters, polymeric vinyl esters, after-chlorinated polymeric vinyl esters, polymeric vinyl ketones and mixtures of these substances-and having incorporated and fixed therein an artificial resin having in its molecule basic groups, which process comprises forming on said textile materials and foils a precipitate of an insoluble metal compound and treating said textile materials and foils with an alkali salt of an acid of the group consisting of perchloric acid, trichloracetic acid,. sultonic acid of fatty alcohols, aliphatic and aromatic sulfonic acids having a long carbon chain, sulfidized phenols, tannin, phosphotungstic acid.

12. A process of producing colorings on artificial textile materials and foils, said textile materials and foils comprising one of the group of organophilic colloids consisting of-cellulose esters, cellulose ethers, cellulose ether esters,

polymeric vinyl esters, after-chlorinated polymeric vinyl esters, polymeric vinyl ketones and colloids consisting of-cellulose mixtures of these substances-and having incorporated and fixed therein an artificial resin with a salt-forming group, which' process comprises dyeing said textile materials and foils in a manner in itseli. known with an organic dyestufi, forming on said textile materials and foils an insoluble precipitate of a colored metal compound ported and fixed therein an artificialresin with a salt-forming oup, which process comprises forming on said textile materials and foils an insoluble precipitate of a metal compound of an organic substance which has not per se the character of a dye, and dyeing said textile materialsv and foils with an organic dye in a mannerin itself known.

14. A process of producing colorings on artificial filaments by printing, said filaments comprising one of the group consisting of-cellulos esters, cellulose ethers, cellulose ether esters,

polymeric vinyl esters, after-chlorinated polymeric vinyl esters, polymeric vinyl ketones and mixtures of these substancesand having incor porated and fixed therein an'artificial resin with a salt-forming group, whichprocess comprises printing said filaments with a printing. paste con-,

taining a soluble metal compoundv capable of forming a colored precipitate with an organic compound which has not per se the character of 4 a dye and developing the color by means of an after-treatment with said organic compound.

PAUL SCI-ILACK. 

